Epoxide, monohydric alcohol-diphenolic acid ester compositions and the modification thereof with aldehyde condensates



adjacent carbon atoms.

EPOXlDE, MONOHYDRIC ALCOHOL-DIPHENOLIC r ACIDESTER COMPOSITIONS AND THE MODI- J FICATION THEREOF WITH ALDEHYDE CON- DENSATES Sylvan Owen Greenlee, West Lafayette, Ind., assignor to S. Cyllohnson & Son, Inc., Racine, Wis.

No Drawing. Application October 2, 1958 Serial No. 764,770

11 Claims. (Cl. 260- 19) This invention relates to new compositions resulting from the reaction of'polyepoxides and monohydric alcohol esters of diphenol carboxylic acids and/ or said compositions modified with aldehyde condensates in regulated proportions to give valuable materials useful in 20 the manufacture of moldings, adhesives, films, etc. The expoxides used in making the new compositions contain an average of more than one epoxide group per molecule and are free from functional groups other than epoxide, carboxyl, and hydroxyl groups. The monohydric alcohol esters of diphenol carboxylic acids are esters having an aliphatic-aromatic structure and containing phenolic hydroxyl groups. The aldehyde condensate modifiers are fusible materials having free reactive sites. The invention includes the initial reaction mixtures as well as the intermediate and final reaction products derived therefrom.

An object of this invention is the production of new compositions from epoxides and diphenolcarboxylic acid esters and said compositions modified with aldehyde condensates to form resins,.varnishes, molding compositions, adhesives, etc.

Another object of this invention is the production of intermediate reaction compositions from the initial reaction mixtures of epoxides and diphenol carboxylic acid esters and said compositions modified with aldehyde condensates, which are capable of further reaction on the application of heat to. form insoluble, infusible products. i r u Another object of this invention is the production of new admixtures of the materials set forth hereinabove which are stable at ordinary temperatures for relatively long periods of time, yet which may be polymerized into insoluble, infusible products with or without the addition of catalysts by the application of heat.

These and other objects and advantageswill appear from the following description, with particular reference to specific examples which are to be considered as illustrative only. V

In general the polyepoxides contemplated for use herein are compounds containing an average of more than one and up to about 20 epoxide groups per molecule. Epoxide groups for the purpose of this specification refer to groups wherein the epoxy oxygen bridges Such compositions, free from functional groups other' than epoxide, carboxyl and hydroxyl groups, are reactive with active hydrogen containing groups including the phenolic groups supplied by the contemplated esters of diphenol carboxylic acids. Typical epoxides which have beenfound to be operable are complex resinous polyepoxides, resinous polyepoxide polyesters, epoxidized natural oils andaliphatic polyepoxides.

The monohydric alcohol esters ofdiphenol carboxylic acids contemplated for use herein are esters of 4,4-bis- .(hydroxyaryl) .pentanoic acids and their equivalent. An

2,907,731 Patented! Qct. 6, 19 59 exemplary ester is the allyl ester of 4,4-bis(4-hydroxyphenyl) pentanoic acid.

The aldehyde condensates are prepared from low molecular weight aldehydes and ammonia derivatives or phenols capable of being condensed with an aldehyde. It is necessary. that the condensate remain soluble and fusible as well as contain reactive methanol groups or an active hydrogen atom attached to some other functional group.

The compositions of the instant invention are prepared by reacting an epoxide with a diphenol carboxylic acid ester and if desired modifying said compositions with the before-mentioned aldehyde condensates, usually in the presence of heat. Having generally described and set forth the objects of the invention, a more detailed description of operable components and reaction conditions will be given.

OPERABLE DIPHENOLIC ACID ESTERS The monohydric alcohol esters of diphenol carboxylic acids employed in this invention are prepared by the reaction of monohydric alcohols with diphenol carboxylic acids such as those described in prior copending application Serial No. 672,356, filed July 17, 1957, entitled Aralkyl Esters]? it u The diphenol carboxylic acids used in preparing the aralkyl esters must have two hydroxyaryl groups attached to a single carbon atom. The preparation of such an aryloxy acid is most conveniently carried out by condensing a keto acid with the desired phenol. To ,the best of applicants knowledge, any keto acid or ester is operable in which a keto group is connected to a carboxy or carboalkoxy radical through an alkylene radical of at least 2 carbon atoms; however, experience in the preparation of bisphenol and related compounds indicates that the carbonyl group of the keto acid should be positioned next to a terminal methyl group in order to obtain satisfactory yields. Further, while a broad class of acids is contemplated such as the keto substituted pentanoic, hexanoic and heptanoic acids, the pentanoic acid, levulinic acid, is preferred since it is readily available.

Prior copending applications, Serial Nos. 464,607 and 489,300 filed October 25, 19 54, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the diphenol carboxylic acid and methods of preparing the same. These materials which are referred to for convenience as diphenol carboxylic acids or by the trade name DPA, consist of the condensation products of levulinic acid or its equivalent and phenol, substituted phenols or mixtures thereof. It is to be understood that the phenolic nuclei of the diphenol carboxylic acids may be substituted with any group which will not interfere with the reactions contemplated herein. Such groups are the halo, nitro and alkyl groups of 1 to 5 carbon atoms. The chloro and bromo phenols are the preferred halogenated materials although it is possible under proper conditions to condense fluoro substituted phenols with a keto acid. Diphcnol carboxylic acids derived from substituted phenols such as the alkylated phenols are sometimes more desirable than the products obtained from unsubstituted phenols due to properties imparted by the substituted groups. For instance, the alkyl groups provide better solvent solubility in selected solvents, flexibility and water resistance. However, the unsubstituted product is usually more readily purified. In the before mentioned condensation reaction between the phenol and keto acid it has been found, as one would expect, that the reaction occurs so that the phenolic hydroxyl group of the diphenol carboxylic acid is in a position para or ortho to the point of attachment of the hydroxyaryl radical to the pentanoic acid. Very little or no condensation position.

Acids A to D inclusive, illustrate typical diphenol carboxylic acids. Proportions expressed are parts by weight unless otherwise indicated. Acidvalues as, used herein represent: the number of. milligrams of" KOHL required to neutralize. aone gram. sample.

Aniixture consisting of; 376 parts of. phenol, 1 16parts of levulinic acid,.and. 250fparts of 3.7 aqueous-hydro: chloric acid was agitated at 4852 C. for 66 hours. The, top layer. wasremoved from. the aqueous. hydrochloric. acid layer by. decantation, Theproduct. was then purifiedby vacuum; distillation of. thevolatile unreacted materials by heating to 180C. at 32. mm. pressure. The residual; product amounted. to. 247' parts- (86.5 theoretical) and had a softening point; of 80 C. and an acid valueof 155.. Purificationof this product by dissolving in'an aqueous bicarbonate solution, reprecipitating with mineral acid, followed by recrystallization from hot water gave a white crystalline compound melting at- 171172 C. with an acidvalue of 196.

Softening points as used herein-were run byDurrans Mercury Method: (Journal. of Oil and Colour- Chemists Association, 12173-5, 1929);

240.5 grams. (2.18 mols) ortho cresol, 15.6- grams (37%) HCl, and 145' grams levulinicacidwere charged toa.2 literround bottom flask equipped with thermometer, reflux'condenser andmechanical agitator. The temperature was raised to 50C. in approximately 1 hour and held in this range'f'or an additional 72 hours. The recoveredmaterialwas washed 6 times with boiling water before steam distilling. Theresultant crude material had 'arracid value of 156, a saponification No; of 206' and was, recovered at 74% oftheoretical based on levulinic acid. I

This crude material was refluxed with aqueous sodium hydroxide for approximately'l hour and the material reacidified, washedand'filtered. The material-was recrystallized'from hot benzene and dried in a vacuum oven. The; resultantimaterial' had an acid value-of 169, theoretical 178-, saponifi'cation'value of 175, theoretical 178 and amelting point, of-1149l'50 C.

363 parts of the ethyl ester. of 4,4-bis 4-hydroxyphenyl) 'pentanoic acid prepared as inA and 344 parts of'sulfonyl chloride were chargedto a 3-necked flask equipped with thermometer, reflux condenser, and mechanical stirrer. The reactionimmediately exothermed and was cooled with a water bath maintaining-the temperature at approximately-25 C. for 1 hour; The reactionchargebecame thick and'then solidified withapronounced temperature rise; The reaction mixture-had a yellowcolor. Excess sulfonyl chloride was removed underslight pressure. The obtained ester had a chlorine content of 21 .38% corresponding to. the addition of approximately 2' chlorine atoms (theoretical equals 18.5%). Thechlorinated ester wassaponified to obtain the corresponding acid.

172-parts DPA prepared as inA and450-parts glacial acetic acid;were chargedto a 3-necked-flask equippedwith athermometer, reflux condenser, and mechanical stirrer. Theresultant solution wastan. in. color.v 264: parts of benzene were addedito' the charge before coolingto C. ini an: ice bath. At this temperature, drop-wise addition of. 85.8 am 70% nitric. acid' diluted with 66 parts. of glacial acetic. acidwas begun. The complete addition occurs at the keto required: 3 hours and 45minutes with: the reaction temperature; never exceeding; 0. C.. The reaction. charge at the; end ofsthe addition. was.a; cleardark. reddish; solution.

The charge was allowed to stir at temperatures between 5' and 20C. for approximately 12 hours. At the end of this time, a heavy orange precipitate had formed. The precipitate was filtered and washed 3 times with distilled water before :it was vacuum dried. The resultant crude material recovered at 84.5% of, theoretical, had an acid value of 488 (theoretical equals 447) and a melting point of 1024 C. The crude material was recrystallized from: amixture ofhot ethanol and Water to giveafine yellow crystalline material having amelting point: of l37.5-140 C., a nitrogen content of 7.20% (theoretical equals 7.44%); and; an acid-.value; of;. 4.45.

The monohydric alcoholsawhich. may. be. used in the esterification ofthev diphenol carboxylic, acids include all stable types, saturated, unsaturated,, waxy or resinous. Operable alcohols thus embrace the saturated alcohols such as methyl, ethyl, butyl, amyl, heptyl, octyl, lauryl and through octadecyl alcohol as well as the more Waxy alcohols containing up to about 36 carbon atoms such as. those derived from carnauba wax. The unsaturated alcohols include allyl, methallyl, 9-undecenyl,' octadecenyl through octadecadienyl al'cohol'andthe longer chain unsaturated al'cohol's up to about 36 carbon atoms. ,A third important operable class comprises the saturated and unsaturated resinous alcohols such. as those derived from rosin and other resinous terpenic materials. The above alcohols are available from a number of commercial sources and can be conveniently derived from vegetable oils, fish oils, natural occurring waxes, etc.

It has beenfound that the esters contemplated for use herein have their properties varied widely by the proper selection of monohydric alcohol used toesterify: the di'- phenol carboxylic acids. The short-chain esters, such as the methyl ester, while providing little plasticizing action, impart'considerable variation to the compatibility of the intermediate products with various ingredients including the polyepoxides. As. the chain length of the monohydric alcohol increases, an increasing amount of plasticiZ- ing actionis obtained so that those products prepared from monohydric alcohols containing, for example, 10 or more carbon atoms in the chain, are'highly plasticized'. Resinouscompositions plasticized in this manner have the plasticizing. groups chemically bondedtherewith andlare thus superior to conventional compositions where the plasticizers are only physically mixed. Such plasticizing groups cannotibe leached out and do not evaporate from films containing the same, and also contribute superior flexibility and toughness. as well as chemical resistance.

As with the saturated alcohols, the. unsaturated monohydric; alcohols contribute variation in miscibility with otheringredients and depending on the chain length, plasticizing action. Inaddition, however, these alcohols contribute the olefin groups which are subject to polymerization. These olefin groups can then be used, by proper formulation, as functional groups for polymerization to infusible, insoluble products by oxidation, such as exposure' of'thin protective coating films to air for long periods of time or by the. application of heat; The use of long chain unsaturatedalcohols, such as the products prepared by selective ester group reduction of unsaturated alcohols, when incorporated as the diphenol carboxylic acid ester in: these compositions, contribute. greatly to. the

gloss characteristics of protective coatings made from thesecompositions.

-It is therefore apparent from the above disclosure that the monohydric alcohols contemplated for use in making the diphenolic 'esters disclosed herein are relatively noncritical. The monohydric alcohol selected is to a large extent dependent upon the end use and. final characteristics desired in the composition. Thus, operable alcohols can be described as those capable of esterifying a diphenol carboxylic acid and free of competing functional groups. Usually these will be alcohols containing only the elements carbon, hydrogen and oxygen. However, alcohols containing amino, nitro, sulfo, etc. substituted groups are. not excluded so long as they do not interfere with the contemplated reactions and are equivalent to the above disclosedalcohols for purposes of the instant invention.

The diphenol carboxylic acid esters are conveniently prepared by methods well known in the art. The higher molecular weight esters can be made by direct heating at temperatures of from 170-275 C. under conditions where the water produced during the condensation is continuously removed as it is formed. The water removal can be accomplished by simply permitting it to volatilize during the condensation or the removal can be facilitated by bubbling an inert gas, such as nitrogen or carbon dioxide, through the reaction mixture or by the use of an inert solvent. The esters of low molecular weight or volatile alcohols can be prepared by suitable alterations of the above general procedure. This will become apparent from the following examples.

Examples 1 to 9 inclusive illustrate the preparation of a selected group of diphenol carboxylic acid esters. It is to be understood that the examples are illustrative only and are not meant to limit the herein disclosed invention. Further, it should be appreciated that in all instances it is not necessary to completely purify the esters. Minor amounts of impurities or unreacted reactants have not been found to effect the final composition obtained therefrom. Proportions as used in the following examples are parts by weight unless otherwise.

indicated.

Example 1 A mixture of 1000 parts of 4,4-bis(4-hydroxyphenyl)- pentanoic acid, 800 parts of methanol, and 3 parts of p-toluenesulfonic acid was refluxed 18 hours and poured into 6400 parts of methanol. To this solution 24,000 parts of water were added and the ester crystallized out on standing. The product was collected by filtration and dried in an oven at 150 C. to give 1010 parts of methyl 4,4-bis(4-hydroxyphenyl) pentanoate. This material was recrystallized from water or a mixture of methanol and water to give the pure ester melting at 13l-2 C. and having a saponification value of 186 (theoretical equals 187). 1

Example 2 A mixture of 572 parts of a diphenol carboxylic acid, prepared from phenol and levulinic acid, and 600 parts of allyl alcohol in a 3-neck flask provided with a thermometer, a mechanical agitator, and reflux condenser was refluxed for a period of 14 hours. The condenser was changed for collection of distillation and the excess allyl alcohol was removed by heating to 150 C. during which time a water leg vacuum of about 30 mm. pressure was applied. The product had an acid value of 12. Acid value is defined as the number of milligrams of KOH necessary to neutralize one gram of sample.

Example 3 A mixture of 286 parts of a diphenolcarboxylic acid, prepared from phenol and levulinic acid, and 268 parts of Makanol 8 (an alcohol produced by Stepan Chemical Company prepared by reduction of soyabean oil and having a specifiediodine value range of 138l54, a hygive refluxing at the esterification temperature. The continuously agitated mixture was heated at 205-240 C. for 4%. hours and held at 240 C. for an additional 30 minutes during which time a water leg vacuum of about 30 pressure was applied to remove the last traces of xylene. This product had an acid value of 6.

Example 4 A mixture of 286 parts of a diphenol carboxylic acid, prepared from phenol and levulinic acid, and 268 parts of Makanol 9 (an alcohol produced by Stepan Chemical Company prepared by reduction of linsed oil and having a specified iodine value range of 193-225, a hydroxyl value of 204-209, an average molecular weight of 265.3, and containing 91% unsaturated alcohols and 9% saturated alcohols) in a 3-neck flask provided with a thermometer, a mechanical agitator, and reflux condenser attached through a water trap was gradually heated to 175 C. A suflicient amount of xylene was added to give refluxing at the esterification temperature. The continuously agitated mixture was heated at 180-220 C. for a period of 7 /2 hours and then taken to 240 C. for an additional 30 minutes duringwhich time awater leg vacuum of about 30 mm. pressure was applied to remove the last traces of xylene. This. product had an acid value of 5. 1

Example 5 In a manner similar to that followed in Example. 3 286 parts of 4,4-bis(4-hydroxyphenol) pentanoic acid and 270 parts of Stenol, a commercialgrade of stearyl alcohol marketed by E. I. du Pont de Nemours, were reacted to give a product having an acid value of 13.

Example 6 In a manner similar to that followed in Example 2 286 parts of 4,4-bis(4-hydroxyphenol) pentanoic acid and parts of 2-ethyl hexanol were reacted to give a prodnot having an acid value of 20.

Example 7 A mixture of 177 parts of the chloro diphenolcarboxylic acid of C and 74 parts of n-butyl alcohol was charged to a round bottom 3-necked flask fitted with a mechanical agitator, thermometer and reflux condenser. Over a period of /2 hour the temperature was raised to 110 C. at which temperature the refluxing began. Over Example 8 188 parts of the nitro diphenol carboxylic acid of D and 65 parts of n-octyl alcohol were charged to a round bottom flask fitted with an agitator, thermometer and reflux condenser. The temperature was raised to C. over a period of approximately 30 minutes. At this temperature a water trap was inserted between the reaction flask and reflux condenser in order to remove the water of condensation. The temperature was increased to 200 C. over a period of approximately 6 hours and held for approximately 5 hours before the final traces of the octyl alcohol were removed by vacuum distillation. The resultant product was a soft resinous material with 7 anacid -value of 20 and an ester number of 101 (theoret ic'al equals 115).

l 2 Example 9 A-mixtureof3l4 parts of the ortho cresol DPA of B and 194 parts of lauryl alcohol was charged to a round bottom flask fitted with thermometer, mechanical agitator,

reflux condenser and water trap. The temperature was acids" canbeusd including"chloro, bromo, nitro and alliylgfoupsof'l to carbon atoms exemplified by 4,4- bis('4-hydroxyj-3=ethyl phenyl) pentanoic acid, 4,4-bis(4- hydroxy-T 5- is'o'propyl phenyl) pentanoic acid, 4,4-bis(4- hYdroiiY-Z-ethyl phenyl) pentanoic acid, 4,4-bis(2-hydroxy 4 b utyl'phenyl) penta'noic acid, 4,4-bis(4-hydroxy- 2',5diar'r '1'yl" phenyl) p'entanoic acid, 4',4-bis(4-hydroxy-3-' fiit'ro phen'y'l) pentanoic acid; 4,4-bis (2-hydroxy-3-nitrop'lien'yl') pentanoicacid; 4,4-bi's(4'- hydroxy 3 methyl pfienyiy entanoic acid, 4,4-bis(4-hydroxy-3-amyl phenyl) pfitanoidaci'd, 4,4-bis(4-'hy'droxy-3-chloro' phenyl) pentafieie acid, 4 4 hydroxyphenyi -4- 4-hydroxy:3-am 1 pliefiyl) pentanoic acid, 4-(4-hydroxyphenyl)-4-(2-hydroxy-4-chlorophenyl) pentanoic acid, 4 -(4 hydroxy phenyl) 4 (4-hydroxy-3,'5'-dibfomo phenyl) pentanoic acids: 4-'(4-hydroxyphenyl)-4 (2-hydroxy-4-nitro' phenyl) pentanoic acid, 4-'(4-hydr'oxyphenyl) -4'- (4-hydroxy-3-sulfo plienyl) pentanoie' acid, 4-(4-hydroxyphenyl)-4-(2-hy drox-y-3,-5 dirnethylphenyl) pentanoic acid, 4,4-bis(2-hydroxy-4-butyl 'phenyl)" pentanoic acid, 4,4-bis(2-hydroxy- 5 methyl-3 chloro phenyl)- pentanoic acid, -4,4-bis(4-hy droxy-3,5-dibromo phenyl) pentanoic acid, 4,4-bis (4- hydroxy-3,5 -dinitro phenyl) pentanoic acid,-4,4 -bis(2-hydroxy-3 nitro-S methyl phenyl) pentanoie aeid -4A- bisQ4P hydroxy-3-methyl-5 chloro phenyl) pentanoic= acid;-,5,'5=- bis(4-hydroxy 'phenyl) hexanoic acid, 5,5-bis(4=-hydroxy-; S-methyl phenyl) hexanoic acid, 5 ,5 -bis(4-hydroxy-3-nitro phenyl) hexanoic acid, and 5,5-bis(4-hydroxy=3-chlorophenyl)hexanoic acid.- v

In Examples 1 to 9 inclusive other monohydric alcohols can be used including ethanol, propanol, isopropanoL -pn'a penol, pentanol, heptanol, decyl alcohol, tetradecanol,-2'- ethyl butanol, heptadecanol, methallyl alcohol, oleyl-alcqhol; amino methylpropyl alcohol,-octadecadienyl alcohol;

benzyl alcohoL-cetyl alcohol and Z-phenylethanoh- OPERAB I LE E'POXIDES Illustrative of the epoxide compositions which- Inay le employed in this invention are the complex epoxide resins which are polyether derivatives of polyhydr'ic phenols with such polyfunctional coupling agents" as polyhalohydrins, polyepoxides, or epihalohydrins. These compositions maybe described as polymeric polyhydric alcohols having alternating aliphatic chains andaryl nuclei connected to each other by other linkages, containing terminal epoxide groups and free from functional groups l olyhydric phenol and an epihalohydrin bis(hydroxyphenyl)isopropylidene excess epi'chlorohydrin' O O omonom-F-o eomononorn o (I)OH;C H CH,

aqueous alkali 1 CH! CH; 12 C CH1 I Piilyljydr'id pheiiol'a'nd a pblyepoxide bis(hydroxypheny1)isopropylidene excess butylene dioxide 1 OH; HCHOHCH1--O OCH1CHOHOEOHCH -O (FCH OHOHCHCH, heat A 5 CH3 CH3 7L CH3 CH3 If P olyhydricphenol and a polyhalbhydrin-bis(hydroxypheny1)isopropylidene excess alpha-glyceroldichlorohydrin ({HkHCHLO oomonondmJ-m come lion,

aqueous alkail 0H on, nofl on, m

As' used in the above formulas, It indicates the degree of polymerization depending on the molar ratio of reactantsf As can be seen from these formulas, the complex epoxide resins used in this invention contain terminal epoxide groups and alcoholic hydroxyl groups attached to the aliphatic portions of the resin, the latter being formed by the splitting of epoxide groups in the reaction of the same with phenolic hydroxyl groups. Ultimately, the reaction with the, phenolic hydroxyl groups of the polyhydric phenols is generally accomplished by means ofepoxide groups formed from halohydrins by the loss of hydrogen and halogen as shown by the following equation:

Other epoxide compositions which may be used include the polyepoxide polyesters which may be prepared by I esterifying"tetrahydrophthalic anhydride with a glycol and epoxidizing the product of the esterification reaction. In the preparation of the polyesters, tetrahydrophthalic' acid may also be used as well as the simple esters of tetrahydrophthalic acid such as dimethyl and diethyl esters. There is a tendency with tertiary glycols for dehydration to occur under the conditions used for esterification so that generally the primary and secondary glycols are the most satisfactory in the polyester formation. Glycols which may be used in the preparation of this polyester composition comprise, in general, those glycols'having 2 hydroxyl groups attached to separate carbon atoms and free from functional groups which would interfere with the esterification or epoxidation reactions. These glycols include such glycols as ethylene glycol, diethylene glycol, triethylene glycol, tetrarnethylene glycol, propylene glycol, polyethylene glycol, neop'entyl glycol, and hexamethylene glycol. Polyepoxide polyesters may be prepared from these polyesters by epoxidizing the unsaturated portions of the tetrahydrophthalic acid residues in the polyester composition. By properly proportioning reactants in the polyester formation and regulating the epoxidation reaction, polyepoxides having up to 12 or more epoxide groups per molecule may be readily prepared. These polyepoxide polyester compositions as well as their preparation are more fully described in a copending application having Serial No. 503,323, filed April 22, 1955. i

Polyepoxide compositions useful in this invention also include the epoxidized unsaturated natural oil acid esters, including the unsaturated vegetable, animal, and fish oil acid esters made by reacting these materials with various oxidizing agents. These unsaturated oil acid esters are longchain aliphatic acid. esters containing frorn'about 1 5 to 22 carbon atoms. These acids may be esterified by simple monohydric alcohols such as methyl, ethyl, or decyl alcohol, by polyhydric alcohols such as glycerol, pentaerythritol, polyallyl alcohol, or resinous polyhydric alcohols. Also suitable are the mixed esters of. polycarboxylic acids and long chain unsaturated natural oil acids with polyhydric alcohols, such as glycerol and pentaerythritol. These epoxidized oil acid esters may contain more than 1 up to 20 epoxide groups per molecule. 1 The method of epoxidizing these unsaturated oil acid esters consist of treating them with various oxidizing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. A typical procedure practiced in the art consists of using hydrogen peroxide in the presence of an organic acid, such as acetic acid and a catalytic material, such as sulfuric acid. More recently epoxidation methods haveconsisted of replacing the mineral-acid catalyst with a sulfonated cation exchange material, such as the sulfonated copolymer of styrene divinylbenzene.

"The epoxide compositions which may be used in prepaving the compositions of this invention also include a suitable catalyst and in turn dehydrohalogenating the.

product'to produce the epoxide composition. The production of these epoxides may be illustrated by the reaction of glycerol with epichlorohydrin in the presence of boron trifluoride followed by dehydrohalogenation with sodium aluminate as follows:

CHZOH O l Fs HOH 3CH2CHCH C1 CHzOH O CHzOCHzCHOHOHgCl OHZOCH2CHCHI O NaAlOz CHOCHzCHOHGHzC] CHOCHZCHCHQ 0 CHZOCHZCHOHCHtCI CHzOCHzCHCH It is to be understood that such reactions do not give pure compounds and that the halohydrins formed and the epoxides derived therefrom are of somewhat varied character depending upon the particular reactants, their proportions, reaction time and temperature. In addition to epoxide groups, the epoxide compositions may be characterized by the presence of hydroxyl groups and halogens. Dehydrohalogenation aifects only those hydroxyl groups and halogens which are attached to adjacent car-- bon atoms. Some halogens may not be removed in this step in the event that the proximate carbinol group has been destroyed by reaction with an epoxide group. These halogens are relatively unreactive and are not to be considered as functional groups in the conversion of. the reaction'mixture of this invention. The preparation of a large number of these mixed polyepoxides is de scribed in the Zech patents, US. 2,538,072, 2,581,464, and 2,712,000. Still other polyepoxides which have been found to be valuable are such epoxide compositions as diepoxy butane, diglycid ether and epoxidized polybutadiene.

Immediately following will be a description or illustration of preparations of polyepoxides which will be used in examples of compositions of this invention.

The complex resinous polyepoxides used in the ex amples and illustrative of the commercially prepared products of this type are the Epon resins marketed by Shell Chemical Corporation. The following table gives the properties of some Epon resins which are prepared by the condensation in the presence of alkali of bis(4- hydroxyphenyl) isopropylidene with a molar excess of epichlorohydrin in varying amounts.

Melting Viscosity I Epoxide Average Epon resin type point, C. (Gardnerequivalent molecular oldt) Weight 1 Based on 40% nonvolatile in butyl Oarbitol at 25 0.

Examples 10 through 12 describe the Example 10 In a- 3-ri'ecked' fiasli' provided with a thermometer; rhechaical agitator and a refluxcondenser attached througha water trap was placed a mixture of 3 mols of tetralrydrophthalic anhydride arid 2 mols of n-butanol. After melting the tetrahydrophthalic anhydride in' the presence ofthe butanol, 2 mols of ethylene glycol-were add'edi The reaction mixture was gradually heated with agitation to 225 C. at which point a sufiicient amount of x nfiewas added to give refluxing at esterification temperature. The reaction mixture was then heated with continuoiisagitation at 225235 C. until an acid value df liwas obtained: Thisproduct gave an iodine value O'f'128;

EPOXIDATION OF THE POLYESTER RESIN Iii a 3 necl ed flask provided with a thermometer, a mechanical agitator, and a reflux condenser was placed 107 parts of the dehydrated acid form of a cationexchange resin (Dowex 50 X8, 50-100 mesh, Dow Chemical Company, a sulfonated styrenedivinylbenzene copolymer containing about 8% divinylbenzene, the percent divinylbenzene serving to control the amount of crosslinkage. The Dowex resins are discussed in publications entitled Ion Exchange Resins No. 1 and Ion Exchange Resins No. 2, copyright 1954 by Dow Chemical Company, the publications having form number Sp32-254 and S p3 1"354, respectively) and 30 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the-acid-. To this mixture was added 200 parts of the polyester resin dissolved in an equal weight of xylene. To the continuously agitated reaction mixture was added dro'p'wise over a period of 45 minutes to 1 hour, 75 parts of 50% hydrogen peroxide. The reaction temperature washeldat 60 C..requiring the application of some external heat. (Insome preparations involving other polyester resins, sufficient exothermic heat is produced during the addition of hydrogen peroxide so that no external heat is' required, or even some external cooling may be required.) The reaction was continued at 60 C. until a milliliter sample of the reaction mixture analyzed less than l milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The acid value of the total resin solution was 42. The percent non-volatile of this solution ar'nounting to 400 parts was 50. This 400 parts of solutionw'as thoroughly mixed with 110 parts of the dehydrated basic form of Dowex 1 (an anion exchange resin of the quaternary ammonium type. Dowex l is a styrenedivinylbenz'ene copolymer illustrated by the formula RR N+CH where R represents the styrenedivinylbenzene rriatrix and R is a methyl group, manufactured by the Dow Chemical Company). The resulting mixture was then filtered followed by pressing as much of the solution as possible from the anion exchange resin cake. This product had an acid value of 4.5 and an epoxide equivalent of 288 based on a non-volatile resin content of The epoxide values as discussed herein were determined by refluxing for 30 minutes a'2-gram sample with 50 milliliters of pyridine hydrochloride in excess pyridine. (The pyridine hydrochloride solution was prepared by adding 20 milliliters of concentrated HCl to a liter of pyridine.) After cooling to room temperature, the sample is then back-titrated with standard alcoholic sodium hydroxide.

Example 11 renewin the procedure'of Example 10', a polyester resin Was prepared from mols of tetrahydrophthalic anhydride, 4 mols of diethylene glycol, and 2 mols of n butanol. This'product had an acid value of 5.3 and an iodine value of 107. "[hisp'olyester resin was epoxidized product, 400 partsof the solution was thoroughly 1 2 in the manner previously describedto give anepoxide equivalent weight of 371 on the non-volatile'contentg The non-volatile content of this resin solutionasprepared-was 40.2%. Example 12 The process or Example 10 was followdib' 6b iil a polyester resin from 1.1 mols of tetrahydrophthalic dride, 1 mol of 1,4-butanediol and 0.2'mol;,of r i butaiiol. The product had an acid value of 8.6. This resin was epoxidized in the same ,manner toii e'an': epoxide equivalent weight of 292 and an acid jvali.le off5q2 on the non-volatile content. The" non-volatile conteiat of this resin solution was 41.9%.

Examples 13 and 14 describe the preparation of epoxidized vegetable oil acid esters.

Example 13 (a) Preparation of alkyd resin.T oa with a condenser was added 290 parts of white refined, soya bean oil. While bubbling a continuous stream pt nitrogen through this oil the temperaturewasjraised-to 250 C., at which temperature-0.23 part of lithargewas added and the temperature held at 2507 for;5 minutes. While holding the temperature above 218 C-.,-6 8;part s' of technical pentaerythritolwasa-dded; after Which-the temperature was raised to 238 C. and held until ga mifle. ture of 2 /2 parts of the product'andlpart' of methyl alcohol showed no insolubility (about-=15 minutes);- At this point 136 parts of phthalic-anhydride' was added andthe temperature gradually raised to 250 C.-an'd held'at this temperature for 30 minutes. At this point'the-con denser was removed from the kettle and the pressure "re" duced somewhat by attaching to a water aspirator evaicuat ing system. With continuous agitation ;the' mixture was then held at 250 C. until the acid value had reaehedlOrS; At this point the resin was thinned-with xylene to -4 8-%' non-volatile content having aviscosity' ofH (Gardner Bubble Viscosimeter). (b) Epoxidatiorv of a soya bean o'il acid m odifiedalky'd resin.ln'a 3-neck flask provided with athermoinetergh mechanical agitator and a reflux condei senwas placed 70 parts of dehydrated acid'form of a'ca'tioncxcha'flg resin (Dowex 5OX8) and 15 parts'g-lacialacetic acid The mixture of cation exchange resin and acetic acid allowed to stand until the resin had'completely talie the acid. To this mixture was added 315-'parts (if the alkyd resin solution described in the above paragraph ahd 190 parts of xylene. To the continuously"agitated: 3 tion mixture was added dropwise 38 part's'fo'f 50% 119.110 gen peroxide. The reaction temperature washeld a't fih" C. until a milliliter sample of the ractio mix analyzed less than one milliliterof 0.1 Nsodiuiif fate in an iodometric determination of hydrogen p roiiidei The product was then filtered, finally'lpies sin tli exchange resin filter'cake; The epoxideeqiiival'enfoiitlie non-volatile content was 475. f In order to remove the free acidity froii i'thep with parts of the dehydrated basic form of (an amine type anion exchange resin)"; The mixture was then filtered, followed by pressing of the solution as possible from the anion exehafig'e'resm cake.

Example 14 Admex '710, an epoxidized soyabean oil having anequivalent Weight to an epoxide of 263,- was dissolvedfin methyl ethyl ketone to a non-volatilecontent 0f--50%; Admex 710, a product of the Archer-Daniels-Midland Company, has an acid value of 1, a visc0sity:of-3.'3 strokes: at 25 C. and an average molecular weight of 937. a

Examples 15 and 16 describe the preparation of 'iliphatic polyepoxides.

Examlple 15 In areaction vessel provided with a mechanical stirrer and external cooling means was placed 276 parts of glycerol and 828 parts of epichlorohydrin. To this reaction mixture was added 1 part of 45% boron trifluoride ether solution diluted with 9 parts of ether. The reaction mixture was agitated continuously. The temperature rose to 50 C. over a period of 1 hour and 45 minutes at which time external cooling with ice water was applied. The temperature was held between 50 and 75 C. for 1 hour and 20 minutes. To 370 parts of this product in a reaction vessel provided with a mechanical agitator and a reflux condenser was added 900 parts of dioxane and 300 parts of powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to 92 C. over a period of 1 hour and 50 minutes, and held at this temperature for 8 hours'and 50 minutes. After cooling to room temperature, the inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at 20 mm. pressure to give a pale yellow product. The epoxide equivalent of this product was determined by treating a l-gram sample with an excess of pyridine containing pyridine hydrochloride (made by adding 20 cc. of concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20 minutes and back-titrating the excess pyridine hydrochloride with 0.1 N sodium hydroxide using phenolphthalein as indicator and considering one HCl as equivalent to one epoxide group. The epoxide equivalent on this product was found to be 152.

Example 16 In a 3-necked flask provided with a thermometer, mechanical agitator, reflux condenser and dropping tunnel was placed 402 parts of allyl glycidyl ether. With contihuous agitation the temperature was raised to 160 C. at which time one part of a 60% solution of methyl ethyl ketone peroxide dissolved in diethyl phthalate was added. The temperature was held at 160-165 C. for a period of 8 hoursyadding one part of the methyl ethyl ketone peroxide solution each 5 minutes during the 8-hour period. After the reaction mixture had stood overnight, the volatile ingredients were removed by vacuum distillation. The distillation was started at 19 mm. pressure and a pot temperature of 260 C. The volatile material was finally removed at a pressure of 3 mm. and a pot temperature of 50C. The residual product had a molecular weight of 418, and an equivalent weight to epoxide content of 198. The yield amounted to 250 parts.

OPERABLE ALDEHYDE CONDENSATES Two general classes of aldehyde condensates are contemplated for preparing the modified products of this invention, those prepared from ammonia derivatives and those derivedfrom phenols, with the choice being dependcut on the end uses and characteristics desired. For instance, if the end use were to be a white enamel, the ammonia derivative-aldehyde condensates would probably be chosen because of. their extremely light initial color and their good color retention. The phenols are somewhat darker in color and have a tendency to yellow upon aging. For the most desirable non-polar solvent solubility, the phenol-aldehyde condensates would be the proper choice since the ammonia derivative-aldehyde condensates usually require some butanol and xylol present to give the desirable solubility. For certain applications, the butanol odor is objectionable and attimes butanol is incompatible with other resins which are used. Adhesion to metals also appears to be better in the phenolaldehyde condensates and in addition have a price advantage.

,The aldehyde-ammonia derivative condensation products are formed by the reaction of aldehydes with amines or amides such as urea, thiourea, and their derivatives,

melamines and sulfonamides. It is necessary that the ammonia derivative contain at least one NH group. Thus nitriles and tertiary amines which are also con sidered ammonia derivatives are excluded. Otherwise the definition reads on amides and primary and secondary amines. It is well known that such materials including a number of their derivatives react with aldehydes to form aldehyde-amine or aldehyde-amide condensates. Exemplary derivatives are substituted urea, thiourea, or melamine such as the long-chain 'alkyl-substituted materials which impart oil, or organic solvent solubility. Suitable sulfonamides include aromatic mononuclear sulfonamides such as toluene sulfonamide, polynuclear sulfonamides such as naphthalene sulfonamide, sulfonamides of aromatic polynuclear ethers and monoor polyfunctio'nal sulfonamides. In addition to melamine, other operable ammonia derivatives, containing the azide bridge'are the amino diand triazines.

' 1n the condensation of aldehydes with the organic ammonia derivatives, initially the reaction appears to be the addition of aldehyde to the organic ammonia derivative to form primarily intermediate alkylol compounds. These compounds will further condense to: form more resinous materials, combining with each other through alkylene bridges formed between the nitrogen atoms of the compounds.

In the alkylol condensate and in the more condensed products of anadvanced stage of condensation, there are hydrogen atoms present in the hydroxyl groups which have been formed in the production of the alkylol condensate and which have not been destroyed by further condensation. There are also an appreciable number of hydrogen atoms attached to nitrogen atoms of the amideor amine groups present in the condensation products. These hydrogens contained in the hydroxyl groups and the amide or amine groups are active Withrespect to epoxide groups and will react therewith in the reaction mixtures of this invention to form complex, crosslinked products,

In general, the condensation jproducts of ammonia derivatives and aldehydes contemplated herein are the partial and intermediate reaction or condensation prod ucts of aldehydes, particularly formaldehyde, with amines or amides, or mixtures thereof. The condensate can be in its monomeric form Whichis essentially an alkylol or polyalkylol product or it may be highly condensed. It is suitable as long as it is still fusible and is soluble in or compatible with the epoxide composition and the diphenol carboxylic acid ester composition with which it is to be reacted. The reactions which produce such con densation products involve the removal of amino or amido hydrogen atoms from the ammonia derivative. Therefore, it should be appreciated that an ammonia derivative as stated hereinbefore, in order to be suitable for condensation with an aldehyde, must contain at least one hydrogen atom attached to the nitrogen atom. Thus, the condensates may be made by various processes known in the art for the manufacture of aldehyde-ammonia derivative resins, resulting in water-soluble, alcoh01-soluble or oil-soluble types.

Many of the commercial products derived from the reaction of urea, thiourea, or melamine with formaldehyde are mixed products made by reacting the formaldehyde with mixtures of these materials. Such composite or mixed reaction products can advantageously be used for reaction with the epoxides and the diphenol carboxylic acid esters according to the present invention. In addition, many of the present day commercial resins derived from aldehydes and urea, thiourea, or melamine, or a mixture thereof, are prepared in the presence of alcoholic or other solvents which take part in the reaction and become an integral part of the resulting resin composition. This is illustrated by the products prepared in the presence of butyl alcohol in which case the butyl alcohol to some extent condenses with the alkylol groups of the aldehyde condensate to. i give butyl ethenresidues as atpart of-the final-composition; Such modified productsare'also -suitable. 'In some cases it *may be-d'esirable to -'us'e 'an ammonia derivative-aldehyde condensate which is completely soluble 'in a-commonysolvent or amixture of solvents used to, dissolve the epoxide'and the diphenol carboxylic' acid ester. Solutions prepared-inthis manner can'be applied asa-coating and'the'solvent subsequently evaporated before the main reaction involving the Example *17' a- 3 liter 3 neck flask provided with a mechanical ous agitation the reaction mixture was heated to reflux temperature and the refluxing continued fora period of lhour. At this point a water trap was placed between the reflux condenserand flask and filled with'toluene. Distillationwas continued until 3 15 'parts of water were removed from the reaction mixture. The resulting mixture was cooled to room temperature, filtered, and 1030 parts ofa clear, water-white syrupy liquid isolated.

Examplc'18 The procedure of a preparation including the water removalwasthesame as that used in Example ,1]. A mixtureof 304parts of thiourea, 960 parts of 37% aqueous formaldehyde, and '800 parts of n-butyl alcohol was used to give a final yield of 1214 parts'of a clear, light amber, syrupyproduct.

Example 19 -The procedure of preparation including the removal of water was the same as that used in Example 17. A mixture of 120 parts of urea, 148 parts of thiourea, 950 parts of 37% aqueous formaldehyde, and parts of n-butyl alcohol wasused to give alfinal yield of 1175 parts of a clear, almost colorless, syrupy liquid;

Emmprezo T In a 3-liter 3-neck flask provided with a mechanical agitator, a thermometer, and a reflux condenser was placed378 parts of melamine, 840 parts of 37% aqueous-formaldehyde, and 725 parts of n-butyl alcohol. With continuous agitation the reaction mixture was heated to reflux temperature and the refluxing continued for a period of 30 minutes. At this point a water trap was placed in the distilling column between the flask and the reflux condenser and filled with toluene; The refluxing was continued until a total of 590 partsof water had been removed from the reaction mixture The product amounting to 1342 parts was a clear, water-White, heavy; syrupy liquid.

Example 21 In a 3-liter 3neck flask provided with a'mechanical agitator, a thermometer, and a reflux condenser was placed'l370 parts of p-toluenesul'fonamide and 640 parts of 37% aqueous formaldehyde the pH of which had been previously adjusted to 6.0 with potassium acid phthalate and sodium hydroxide. With continuous agitation the reaction mixture was heated to reflux temperature over a period of 40 minutes and the refluxing continued for a period of 15' minutes. At this point the reaction mixtu'rewas allowed to cool and the Water decanted from the resin. The resin'was washed 3 times with'warrn water and'finally' dehydrated invacuum at 30-50 pressure, using a maximum flask tem erature of90" C, to yield 1245*psits of water-whiteresinous solid,

In Examples 17 to 2 -l inclus ive, the ammonia derivative can be replaced by other materials which have a 1 filletlfb'i hy- NH- gfoup with the free valel iees dro 'en or carbon atbmsb This"tl"1'erefor iiicliid i a'iid prirnary and seconaaiy amines uch' as eft'l'rea thio u re'as, 'rn 1'a"rnines-, Stilfoiitfflitie'S; and flkyl-Siib'fitlifd derivatives thereof. His only necessary-marineinatenar be capable of condensing 'with anald'ehyde I The second class of condensates suitable for 'odi'fyirig" the I compositions heiei'ri describ e"d' those 1 which coii f an reactivephenolic hydfcxy'r' rsups r0 reaction of plienolsand "aldehy d e' ss Q dehyde react to fern? fie pending upon the pr ass. These include premiers such" as naviag both phenolic and alcoholic n xyr'grbup htli products of the diphenolrnethane' typecontaining phenolic hydroxyl r'saps only. The eeaaefis'aaen afpuendrjnh formaldehyde can be cafriedout- "th of a dot ikannecbadensingagents and in eome'ce'sesbY' r bining'; the aldehyde an alkalf'suehas tfi'lffitinl 1 form hexam'ethylerietctranfine' afid 'realetifig' thelatte the phenol. The' phe'r'iol-aldehyde resins tari rar intermediate "stage of reaction are; intended to "be inelfide d in'the term phenOPaldeIiyde condensates as usea Iri'general, the phenol-aldehyde cendeasatessusuwnr have their condensation carried so rat aster soluble and nonreactive. It' is'* preferred in their tion "or the instanrcompositioiis thatrfiey be used at intermediate stage or atastageotreaetionsuch thatfthe'j contain reactive phenolic hydr'exyl groups or phenolic and alcoholic hydroxyl groups. This is desirable in order to permit a proper blending of the phenolaldehyde condensate with the po'lyepoxides"anddiphenol carboxylic acid'ester for subsequentreactl ntherewith.

The phenol-aldehyde condensates may be derived from" mononuclear phenols, poly'nuclear phenols, "rnonohydfie phenols, or polyhydric phenols." The'c'ritic'al requirement for the condensate is that it be conipatible withthe" polyepoxides and diphenol carboxylic acidesters'or'with the two reactantsin a-so'lvent used as'a reactionmedium? The phenol-aldehyde condensate Whi'eh-is"e'ssei1tiaily"'2r polym'ethylol phenol rather than "a polymer may'laeused in the preparation of the new phenol=aldehyde;-poly=' epoxide, diphenol'carboxylic acid ester prddlfctsjor it' may. be used 'after further condensation, in which case some of the methylol groups are usually-consideredto have disappeared in the process "of condensation. variaas so-c'alled phenolic resins which result fromthe reaction of phenols and aldehydes, andparticularlvfromcommdn phenols or cresols and formaldehyde, areavailable as commercial products both of an initial and-intermediate character. Such products includeresins which are readily whale o aj awa 9 r a il a b ejs aaiaa be ad qd w th. h r an h a lrhai l a acid esters and reacted therewith to fdrn'rthe products of as illustrated by p-te 't-b tylpheno pro duce. fusible resins on reaction w 1 h f aldeh thot'tgh fusible condensates are employed, how soluble, inffisibl e prfod'uets res lii'eated coin b ination with the pdiifd's'find ftfiwmmfibl boxylic iaeidestersdescribed; i

perrnan Examples 22 "to 24; inel'usiv'e," '(tsfffii of some or "are operate primal-aldehyde"centi etre; which may be used in combination with the polyepex'ide and dipiienene acidestr's'tq '15 ein described It is to be nest ed thaftlie' three examples as 17 drawn from distinct classes of phenols and are meant to be representativeof the broad class of phenols. Thus, in; Example 22, the phenol is a dihydroxy dinuclear phenol, inEx'ample 23 an alkyl-substituted phenol, and in Example 24 a simple phenol. The examples, therefore, illustrate theunsubstituted monohydric phenols, the substituted monohydiic phenols, and the polynuclear phenols.

Example 22 In a,3-liter 3.-neck flask provided with a mechanical agitator, a thermometer, and a reflux condenser was p1aced912 parts of Bisphenol A, 960 parts of 37% aqueousformaldehyde, and 2.3 parts of oxalic acid. With continuous agitation, the reaction mixture was heated to the reflux temperature and refluxing continued for a period of 1 hour. After permitting the reaction mixture to cool to around 50 C. the water layer was removed by decantation. v The henoI f ormaIdehyde layer was then washed three times with water which in each case was removed by decantation. The last portion of water was removed by distillation at reduced pressure using a water aspirator system which gave pressure around 30-40 mm. The temperature during the removal of this last portion of water ranged from 70-90 C. The product, amounting to 1065 parts, was a clear, heavy, syrupy material.

Example 23 Example 24 Again a reaction procedure including the dehydration step, was the same as that used in Example22. A mixture of 658 parts of phenol, 1400 parts of 37% aqueous formaldehyde, and 6.6 parts of sodium hydroxide was used to give a final yield of 1168 parts of a clear, syrupy product.

In Examples 17 and 24 inclusive, the aldehyde can be replaced by other mono-aldehydes including acetalde hyde, propionaldehyde, n,butyraldehyde, isobutyraldedehyde, valeraldehyde, capronaldehyde, heptaldehyde as well as the more complex aldehydes such as furfural.

In Examples 22 to 24 inclusive, the phenol can be re-:

placed by other phenols including ortho, meta, and para cresol,2,4 xylenol, 3,4 xylenol, 2,5 xylenol, 3,5 xylenol,

2,5 dibutyl phenol, p-phenyl phenol, 2. ethyl-phenol pcyclohexylphenol, 3 isopropyl phenol and p-tert-amylphenol.

GENERAL REACTION CONDITIONS AND CHAR- ACTERISTICS OF THE NEW COMPOSITIONS In making the new compositions, the polyepoxides and diphenol carboxylic acid esters or such compositions modified with aldehyde condensates are admixed in suitable proportions and reaction will proceed merely by the application of heat. More specifically the reaction is effected by heating the mixtures at elevated temperatures, 1 usually in the range of about 75250 C. Catalysts are unnecessary, but in certain cases it may be desirable to speed up the reaction by the use of catalysts, suc h as boron trifluoride adducts, sodium phenoxides, and mineral acid type catalysts.

The reaction mixtures and final reaction products of this invention can be prepared by using varying ratios of epoxide to diphenol carboxylic acid esters. The quantities of reactants employed in a given instance will de pend upon the characteristicsdesired in the final product. Flexible or rigid. materials can be obtained from the properselection of epoxide, diphenol carboxylic acid ester and plienolaldehyde condensate. In general, oper able products are those in which the ratio of epoxide to j 18 diphenol carboxylic acid ester, on an equivalent weight basis, ranges from about 6zl to,1f:6 with the preferred range, because of the general over-all characteristics, being from 2:1 to 1:2. In instances where an aldehyde condensate is usedas a modifier, operable amountson a weight basis of the combined epoxide and diphenolic'acid range up to about 90%, but from a practical standpoint, the preferred percentage is about 10% to 35 Equivaw lent weight as used above refers to the weight of polyepoxide per epoxide group, in the case 'of the polyepoxide, and the weight of the diphenol carboxylic acid ester per phenolic hydroxyl group, in the case of the ester." H

Compositions containing the polyepoxides and, the diphenol carboxylic acid esters or such compositions modified with aldehyde condensates can be used as admixtures or at varying intermediate stages of reaction. The initial admixtures or intermediate reactionproducts which are soluble in common organic solvents may be blended in solution in proper proportions and the solutions then applied as an impregnant for fabrics or paper, or for the formation of protective coating films. Subsequent heating functions to remove the solvent and bring about polymerization to the insoluble, infusible state. For other uses, the initial or intermediate mixture may be used without a solvent, giving directly a composition which, on the application of heat, converts to an infusible, insoluble final product. i

In making the new compositions and products herein described, the polyepoxides and the diphenol carboxylic acid ester or such compositions modified with aldehyde condensates are usually used in regulated proportions without the addition of other materials. However, for certain uses, other components are often advantageously added, including filling and compounding materials, plasticizers, pigments, etc. The compositions which tend to give somewhat brittle products on conversion to the insoluble, infusible state can be advantageously compounded with plasticizers, although for most applications, it is possible to obtain suitable flexibility and toughness by regulating the proportions and types of reacting ingredients, thereby obviating the need for plasticizers.

The application of heat to the mixtures herein set forth involves several chemical reactions. It will be appreciated that the reactions involved are complex and the extent to which each takes place will vary with the temperature used in heat treating, the period of time there- ..for, and with the particular types of polyepoxides, aldehyde condensate, if used, and diphenol carboxylic acid ester chosen. While it is not desired to be limited by any theoretical explanation of the exact nature of these reactions, it seems probable that conversion to the final polymeric productsis accompanied by direct polymerization of the epoxide groups inter se; reaction of the epoxide groups with methylol hydroxyl groups; reaction of the epoxide groups with phenolic hydroxyl groups, and reaction of epoxide groups with active hydrogen attached to a nitrogen atom, all of which take place to some extent simultaneously in forming the final products.

The present invention provides a wide range of reaction compositions and products including initial mixtures of the polyepoxides, aldehyde condensates, and the diphenol carboxylic acid esters, partial orintermediate reaction products of such mixtures and compositions containing such intermediate reaction products as well as final reaction products. Ingeneral, the initial mixtures, as well as the intermediate reaction products unless too highly polymerized, are soluble in solvents of the lacquer type, such as ketone or ester solvents.

In addition to having outstanding physical properties, such as hardness, toughness and flexibility, the final infusibl e, insoluble products have outstanding chemical properties, such as high resistance to oxidation, water, alkali, acids and organic solvents. It has also been observed that the final conversion products possess unusually good adhesion to most surfaces including metal,

glass, wood and plastics. This property of outstanding adhesion tofa wide variety of surfaces gives the subject product s high potential value for use in formulating adhesives. This property is also of extreme value in formulatiug protective coating films for use on many types ofg s urfaces The adhesion characteristics are probably dueto the factthat even in the converted, infusible state, the compositions. contain a relatively high percentage of highly polargroups, such as ether groups, ester groups, and alcoholic and phenolic hydroxyl groups. Despite the high perc'entage of polar groups in the insoluble, infusible products of this invention the tolerance for water is unusually low, apparently due to the high molecular weight and rigid cross-linked structure of the final compositions.

Prior Greenlee applications, Serial Nos. 541,022, 557,835 and 562, 663 filed on October 17, 1955, January 9, 19 56, and February 1, 1956, respectively, relate to conversion products obtained from polyepoxides and diphenol carboxylic acids. The conversion products of this invention are to be distinguished therefrom in that here, the esterification of the carboxyl group removes one functional group from the reaction mixture. Thus, the compositions of this invention are characterized by a lower degree of cross-linking with the epoxide groups and alcoholic hydroxyl groups found in the polyepoxide. This diminished cross-linking is a factor which contributes to a relatively greater degree of flexibility or a lower degree of hardness in-the products of this invention, as compared to'those described in the above applications. additional factor contributing to this property is the presence of the carbon atoms contributed by the alcohols used to make the ester, Although effective plastieization is effected only by the reactively high molecular weight EXPERIMENTAL Examples 25 to 155, inclusive, illustrate the preparation of insoluble, infusible protective coating films from the compositions of this invention; In the preparation of the compositions for heat curing to form the protective coating films, each of the diphenol carboxylic acid esters and the polyepoxides with the exception of epoxidiz ed polyesters were dissolved in methyl ethyl ketone to a non-volatile content of 40-60%. In certain instances it may be desirable to use a small amount of dioxane or similar solvent to help effect the solubilization of the diphenol carboxylic acid esters. The epoxidized polyesters were used at the non-volatile and in the solvent in which they were prepared. The aldehyde condensates were dissolved in a mixture of methyl ethyl ketone and butanol to a non-volatile content of 40-60%. Mixtures of the diphenol carboxylic acid esters and polyepoxides or such compositions modified with aldehyde condensates were found to be stable up to six weeks or more at room temperature. Mixtures of the solutions were spread on panels with a .002 Bird applicator and the films were baked for periods of 30 to 90 minutes at temperatures ranging from 150200. C. Proportions. as used in the following table refer to parts by weight and are based on the non-volatile content of the solutions of reactants.

Film resistance Parts of Parts of Parts of Baking Example polyepoxide DPA ester aldehyde schedule,

condensate min./T. 0. Boiling water 5% aqueous NaOH at 25f O.

16.2 Epon1001. 50E): 1-..- 14th:. 9.1 Epon1001- 5013): 3 144111. do 50Ex 4-... 176 1 9.0 Epon1001 50EX 5.... 168111 12.1 Epon 1001. Ex 168 hr 14.9 Epon1001 Ex 168hr 29 8 Epon 1004 144 hr 33.1 Epon 100 w ramar-mememem 30/175 min. min 30/175 5 hr. mi.n 20 min. 30/175 8 l1r. 6hr. 30 1mm I .30 min. 15 min.

x. x. 15 min. x. 30 min. x. 30 min. x. 30 min. x. 1 hr. 15 min. x. 30 min. x. 3 2 hr. x. 1' hr. 30 min. x. 30min. x. 30 min.

10.0 Ex. 3 45min.

10.0 Ex. 4 3 hr.

5.0 Ex. 30 min 5.0 EX. 4hr.

5.0 Ex. 4 hr.-

10.0 Ex. 5 24 hr;

10.0 Ex. 6 20 min 10.0 Ex. 2 20 min 5.0 Ex. 45/200 4 hr. 30 min- 3 hr.

git. 30/200 2 hr. 20 min. 30 min.

45 200 2hr. 20mm... 30 m.

1 1 Film resistance i Partsot Partsof Parts of Baking Example. .polyepoxide DPA ester aldehyde schedule, 1 Y condensate mi /"13 G. Boiling-water 45% aqueous 1 NaOHat25O.

1.0 Ex. 2 hr. 0.5 Ex. 1.0 Ex. 0.5E 1.0 E 1.0 E r 1.0 E 1.0 E 0.5 Ex.

5.0 3.8 5.0 2.2 5.0 6.4 5.0 1.4 5.0 6.0 5.0 2.8 5.0 4 3.2 8.0 1.0 2. 2.5 5.0 1.0 E 0.5 Ex. 3---- 8.5 5.7E 10.0 Ex. 4 2.0 10 6.6E 5.0 Ex. 1- 1.2 45/175 5 30 k 3.7 E 5 Ex 3-.-- 1.7 Ex. 24 30 5.7 E 10.0 Ex. 5--- 1.6 Ex. 22... ll 7.5 E 10.0 Ex. 5--. 1.8 Ex. 24--- 6.1 E 5.0 Ex. 2;--- 1.1 Ex. 22... 8.0 E 6 1.0 Ex. 4---. 1.0 Ex.24-.. 2.5 Ex. 2.5 Ex. 5--.- 5.0 Ex. 22--- 5.0 Ex. 10 5.3 Ex. 2.1 Ex. 22 59 Ex. 11 1 5.0 Ex. 2.3E 8.9131. 12.. 5.0Ex.2- 1.4. 9.6Ex. 10-- 5.0 Ex. 1---- 1.5 5.4 Ex. 10 "5.0 Ex. 3---- 1.0 E 7.3 1 5.011 1.2 8.8 5.0 1.4 1.0 0.5 8.5 115 8.5 1.0 0.5 115- 9.2 5.0 1.5 117- 9.1 5.0 1.4 118. 5.3 5.0 2.3 119 9.1 5.0 1.4 120. 11. 5.0 1.5. 121 .29. 5.0 3.5 122. 33. 5.0 8.8 128. 12 5.0 1.7 124. 8. 5.0 1.4 9 125- 14. t 5.0 2.0 x. 18--- 125. 5.3 5.0 1.1 x. 18--. 127. 15. 5.0 2.2 17 128; 10. 5.0 1.5 129. 33. 5.0 3.81 130. 44. 5.0 5.0 131. I 1.0 1.0 8.0 132 5.4 5.0 1.0 133 11. 5.0 -1.6 134 5.4 5.0 1.0 135 10. 10. 2.1 135 10. 5.0 1.5 137 73E 1 5.0 1.2 138-- 4.7 Ex.10 5.0 1.9 139-- 5.0 Ex. 11. 3.5 p .9 Ex. 21--.. 140.- 5.0 Ex. 11- 3.6 Ex. 4---. 9 Ex. 141.- 8.0 Ex. 11- 1.0 Ex. 4---- 1 0 Ex. 18--- 142.- 1.0 Ex. 11- 8.0 Ex. 3- 1 0 Ex. 19--- 143 2.5 Ex. 11- 2.5 Ex. 5---- 0 E 144.. 10.1 Ex. 15 145 5.7 Ex. 15- 145-- 3.7 Ex. 15- 147.- 1 311311.16. 148.- 5.0 Ex. 10- 149.- 9.3 Ex. 15 150.. 5.1 Ex. 151 5.7 Ex. 152-- 8.0 Ex. 153,- 1.0 E11,. p 154-. 10.2 Ex. a 155 15.3 Ex.

" 00555115 02 550115025 catalyst.

. 1 Example 156, 65 I p Example 158 4 parts Epon 1001, 25 partsExample :4, and '50 parts 10 ,parts Example 15,; 10 parts Examplefi and 80 Example 18 were chargedito a reaction vessel. and heat parts-Example 19 were charged to areaction vessel and converted mlnutes at 200 C. to give a hard, tough, heat..converted.d30 minutesat .2001? C. Ito. 'giveta hard; 1nfus1ble and msoluble product. tough, 1nfus1ble and 1nsoluble product.

Example 157 Example 159 10 parts Example 10, 10 parts Example 2 and 80 parts 25 parts Example 15, 25 parts Example 3 and 50 parts Example 19 were charged to a reaction vessel and heat Example 19 were charged to a reaction vessel and heat converted 30 minutes at 200 C. to give a hard, tough, converted 30 minutes at 200 C. to give a hard, tough, infusible and insoluble product. infusible and insoluble product.

Example 161 parts of Example 15, 80 parts of Example 6and 10 parts of Example 24 were charged to areaction vessel and heat converted 30 minutes at 200 C. to give a hard, tough, infusible and insoluble product.

Example 162 10 parts of Example 16, 10 parts Example 3 and 80 parts Example 24 were charged to a reaction vessel and heat converted 30 minutes at 200 C. to give a hard, tough, infusible and insoluble product;

Example 163 25 parts of Example 11, 25 parts of Example 2 and 50 parts of Example 23 were charged to'a reaction vessel and heat converted 30 minutes at 200 C. to give a hard, tough, infusible and insoluble product.

Example 164 g 49 parts of Example 14, 50 parts of Example 4 and 30 parts of Example 22 were charged to a reaction vessel and heat converted 30 minutes at 200 C. to give a hard, tough, infusible and insoluble product.

It should be appreciated that the invention is not to be construed to be limited by the illustrated examples. It is possible to produce still other embodiments without departing from the inventive concept-herein disclosed. This application is a continuation-in-part of the Green lee copending applications S.N. 597,360, 609,553, and 610,384, filed July 12, 1956, September 13, 1956, and September 17, 1956, respectively, now abandoned.

It is claimed and desired to secure by Letters Patent:

1. A composition of matter comprising the condensation product obtained by heating (A) an organic polyepoxide having an average of more than one epoxide group'pe'r molecule wherein the epoxy oxygen atom is linked to adjacent carbon atoms and (B) the 4,4 bis(hydroxyaryl) pentanoic acid ester of an aliphatic monohydric alcohol wherein the hydroxyaryl radical is a member of the group consisting of unsubstituted hydroxyphenyl and ring substituted hydroxyphenyl wherein the hydroxy group of said member is in a position other than one meta to the point of attachment of said member to the pentanoic acid,

any substituents-on the hydroxyphenyl being a member selected from the group consisting of chloro, bromo, nitro and alkyl groups of from 1-5 carbon atoms, and

wherein the reactive oxirane groups of (A) and the reactive hydrogens of (B) are present in an equivalent ratio of from 6:1 to 1:6. 1

2. The composition of claim 1 wherein the reactive oxirane groups of (A) and the reactive hydrogens of (B) are present in an equivalent ratio of from about 2:1 to 1:2.

3. A composition of matter comprising'the condensation product obtained by heating (A) an organic polyepoxide having an average of more than one epoxide group per molecule wherein the epoxy oxygen atom is linked to adjacent carbon atoms, (B) the 4,4 bis(hydroxyaryl)pentanoic acid ester of an aliphatic monohydric wherein. the hydroxyaryl radical is a member of the group consisting of unsubstituted hydroxyphenyl and ring substituted hydroxyphenyl wherein the hydroxy group of said member is in a position other than one. meta to the point of attachment of said member to the pentanoic acid, any substituents on the hydroxyphenyl being a member selected from the groupeonsistingof chloro, bromo, nitro and alkyl groups of from 1-5 carbon atoms, and wherein the reactive oxirane groups of- (A) and the reactive hydrogens of (B) are present in an equivalent ratio of from about 6:1 to 1:6, and (C) from 10-35% by Weight of a fusible condensate of a monoaldehyde with at least one organic ammonia derivative selected from the group consisting of urea, thiourea, melamine, j toluenesulfonarnide and alkyl substituted derivatives thereof. 1

4. A composition of matter comprising the condensation product obtained by heating (A) an organic polyepoxide having an average of more than one epoxide group per molecule wherein the epoxy oxygen atom is -linked to, adjacent carbon atoms}, (B) the 4,4 b-is(hy- .-droxyaryl)pentanoic acid ester of an aliphatic monohydric alcohol wherein the hydroxyaryl radical is a member ofthe group consisting of unsubstituted hydroxyphenyl and ring substituted'hydroxyphenyl wherein the hydroxy group of said member is in a position other than one meta to the point of attachment of said member to the pentanoic acid, any substituents on the hydroxyphenyl being a member selected from the group consisting of chloro, bromo, nitro and alkyl groups of .from1-5 car bon atoms, and wherein the, reactive .oxirane groups of (A) and the reactive hydrogens of (B) are present in an equivalent ratio of from about 6:1 to 1:6, and (C) from 10-35% by weight of a fusible condensate of a mono-1 aldehyde with a phenol. Y

5. The composition of claim 2 wherein the pentanoic acid is 4,4-bis(4-hydroxyphenyl) pentanoic acid.

6. The composition of claim 2 wherein the hydroxyaryl radical of the pentanoic acid is alkyl substituted.

7. The composition of claim 2 wherein the mono-' hydric alcohol contains only carbon, hydrogen and oxygen and is free of reactive groups other than hydroxyl.

8. The composition of claim 2 wherein said polyepoxide (A) isa complex epoxide whichis a polymeric polyhydric alcohol having alternating aliphatic chains and aromatic nuclei united through ether oxygen and 1 terminating in oxirane substituted aliphatic chains.

, 9. The composition of matter of claim 2 wherein said polyepoxide (A) is an epoxidized polyester of tetrahydrophthalic acid and a glycol, wherein the epoxy oxygen atoms'are each linked to adjacent carbon atoms in the nucleus of said acid.

10. The-composition of matter of claim 2 wherein said polyepoxide (A), is an epoxidized' ester of an unsaturated natural fatty oil acid containing about 15-22 carbon atoms, and having its reactive groups selected from the class consisting of oxirane and hydroxy.

11. The composition'of matter of claim 2 wherein said polyepoxide (A) is an aliphatic polyepoxide selected from the group consisting of bis(glycidyloxy) butene, triglycidyl glyeeryl ether, diepoxy butane, and diglycide ether.

Bader et aL: J.A.C.S., vol. 76, pp. 4465-4466 (Sept. 5, 1954). (Copy in Scientific Library.)

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,907,731

October 6, 1959 Sylvan Owen Greenlee It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 22, for expoxides read -epoxides; column 6, line 18, for linsed read linseed; lines 36 and 43, for LA-bis (4-hydroxyphen0l) pentanoic acid, each occurrence, read 4,4-bis(4-hydroxyphenyl)pentanoic acid-; column 9, line 64:, for consist read c0nsists-; column 10, lines 24: to 30, the right-hand portion of the equation should appear as shown below instead of as in the patent:

O OHgOCHaHEH:

O HO CHZKHBH:

CHaOCH2C H CHn column 11, line 54, for RR' N+CH" read RR N+OH" column 12, line 72, for strokes read stokes; column 16, line 55, for epoxide read --epo;xides; line 74 and column 18, line 6, for diphenolic acid, each occurrence, read -Diphenolic Acid; column 23, line 55, after from insert about-; line 66, before wherein insert alcoh01-.

Signed and sealed this 17th day of May 1960.

Attest:

KARL H. AXLINE, ROBERT C. WATSON, Atteatz'ng Oyficer. Oomz'ssz'oner 'of Patents. 

1.A COMPOSITION OF MATTER COMPRISING THE CONDENSATION PRODUCT OBTAINED BY HEATING (A) AN ORGANIC POLYEPOXIDE HAVING AN AVERAGE OF MORE THAN ONE EPOXIDE GROUP PER MOLECULE WHEREIN THE EPOXY OXYGEN ATOM IS LINKED TO ADJACENT CARBON ATOMS AND (B) THE 4,4 BIS(HYDROXYARY) PENTANIOC ACID ESTER OF AN ALIPHATIC MONOHYDRIC ALCOHOL WHEREIN THE HYDROXYARYL RADICAL IS A MEMBER OF THE GROUP CONSISTING OF UNSUBSTITUTED HYDROXYPHENYL AND RING SUBSTITUTED HYDROXYPHENYL WHEREIN THE HYDROXY GROUP OF SAID MEMBER IS IN A POSITION OTHER THAN ONE META TO THE POINT OF ATTACHMENT OF SAID MEMBER TO THE PENTANOIC ACID, ANY SUBSTITUENTS ON THE HYDROXYPHENYL BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF CHLORO, BROMO, NITRO AND ALKYL GROUPS OF FROM 1-5 CARBON ATOMS, AND WHEREIN THE REACTIVE OXIRANE GROUPS OF (A) AND THE REACTIVE HYDROGEN OF (B) ARE PRESENT IN AN EQUIVALENT RATIO OF FROM 6:1 TO 1:6. 